UvA-DARE is a service provided by the library of the University of Amsterdam (https://dare.uva.nl)
Photoinduced processes in dendrimers
Dirksen, A.
Publication date
2003
Link to publication
Citation for published version (APA):
Dirksen, A. (2003). Photoinduced processes in dendrimers.
General rights
It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s)
and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open
content license (like Creative Commons).
Disclaimer/Complaints regulations
If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please
let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material
inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter
to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You
will be contacted as soon as possible.
Chapterr 1 Shining Light on Dendrimers 1
11 Introduction 1 1.11 The Purposes behind the Development of Photoactive Dendrimers 2
22 Dendrimers as Luminescent Materials 5 2.11 Interchromophoric Interactions in Periphery-Functionalized Dendrimers 5
2.22 Core-Functionalized Dendrimers 6 2.33 Sell-Organized Fluorescent Dendritic Materials 12
33 Photoisomerization of Azobenzene-Containing Dendrimers 14
44 Energy Transfer 19 4.11 Excitation Energy Transfer among Chromophores at the Periphery 19
4.22 Light-Harvesting (Antenna Effect) 20 4.33 Single Molecule Spectroscopy (SMS) 28 55 Photoinduced Electron Transfer (PET) 30 5.11 (Organic) Light Emitting Diodes ((O)LEDs) 34
66 Summary and Outlook 36 77 Scope and Contents of this Thesis 37
88 References 39
Chapterr 2 The Photoactivity and pH Sensitivity of Methyl Orange-Functionalized
Poly(propyteneamine)) Dendrimers 49
2.11 Introduction 50 22 Results and Discussion 52
2.11 Photophysical Properties 52 2.22 Isomerization 52 2.33 pH Sensitivity 55 33 Conclusions 57 44 Experimental Section 58 4.11 Materials 58 4.22 Synthesis 58
2.4.33 UV-Vis Absorption and Fluorescence Spectroscopy 58
2.4.44 pH Sensitivity 58 2.4.55 Kinetics of the Z to E Isomerization 58
2.55 References 59
Chapterr 3 Ultrafast Photoinduced Electron Transfer across Hydrogen Bonds of a
Self-Assembledd Donor-Acceptor System 61
3.11 Introduction 62 3.22 Results and Discussion 64
3.2.11 Synthesis and Characterization of Guest and Host Molecules 64
3.2.22 Photophysical Properties of B A rrH l and G2 64
3.2.33 Characterization of PF6 H 1 G 2 in Acetonitrile-d3 by ! H NMR 65
3.2.44 Diffusion Ordered NMR Spectroscopy (DOSY) 66
3.2.55 Photophysical Study for B A rrH l - G 2 67
3.33 Conclusions 72 3.44 Experimental Section 74
3.4.11 Solvents and Starting Materials 74
3.4.22 Synthesis 74 3.4.33 Instrumentation 77 3.4.44 Determination of the Association Constant (Kass) of PF6-H1-G2 in Acetonitrile-d^ 78
3.4.55 Determination of the Association Constant (Kass) of B A rrH l * G 2 in CH2C12 78
3.55 References and Notes 79
Chapterr 4 Multiple Recognition of Barbiturate Guests by "Hamilton"
Receptor-Functionalizedd Dendrimers 83
4.11 Introduction 84 4.22 Results and Discussion 87
4.2.11 Synthesis and Characterization of the HR-dendrimers 87
4.2.22 Determination of the Association Constants (Kass) 88
4.2.33 Photophysical Properties of GO and the HR-Dendrimers (Gx; x = 1.2.3. 4) 89
4.2.44 Energy Transfer in the Gx-B2 (x = 0. 1.2. 3. 4) Complex 92
4.2.55 Competition Experiment between B2 and Bl 96
4.33 Conclusions 96 4.44 Experimental 97 4.4.11 Synthesis 97
4.4.22 Instrumentation 97
4.4.33 Determination of the Quantum Yields of Emission 98
4.4.44 Determination of the Binding Constant of Bl to GO Using
]H NMR Spectroscopy 98
4.4.55 Determination of the Binding Constant of B2 to GO Using Fluorescence
Spectroscopyy 98
4.4.66 Energy Transfer Study of Gx <x = 1, 2, 3, 4) with B2 98
4.4.77 Competition Experiment between Bl and B2 98
4.4.88 Deprotonation of B2 by the Poly(propyleneamine) Core 98
4.55 References 99
Chapterr 5 Simultaneous Selective Binding of Different Guests within Dendrimers:towardss Well-Defined Functional Supramolecular Assemblies 103
5.11 Introduction 104
5.22 Results and Discussion 105
5.2.11 Design of the Dendritic Template 105
5.2.22 Synthesis and Characterization of the Guest Molecules 107
5.2.33 Selective Binding of Guests in Model Systems 109
5.2.44 Characterization of the Assemblies Formed between the HR-Dendrimers and the
Fluorinatedd Urea Guest Molecules by NMR Spectroscopy 111
5.2.55 Characterization of the Host-Guest Complex between the HR-Dendrimers, AQ,
andd Barbital Using NMR Spectroscopy 119
5.2.66 Approach for the Construction of the Photoactive Assembly 122
5.2.77 Photophysical Properties of the Host-Guest Complex
G2-4AQ-2[Re(Br)<CO)
3(barbi-bpy)]] 123
5.33 Conclusions 125
5.44 Experimental 126
5.4.11 Solvents and Starting Materials 126
5.4.22 Synthesis 126
55 4 3 Instrumentation 131
5.4.44 NMR study of the Fluorinated Guest Molecules 131
5.4.55 NMR Study of AQ 132
5.4.66 Photophysical Study of the Host-Guest Complex
G2-4AQ-2[Re(Br)(CO)
3(barbi-bpy)]] 132
Appendixx 137
Summaryy 143
Samenvattingg 149
Samenvattingg voor niet-chemici 155
